Azo compounds and material colored therewith



doscph lll iclrey and William lhl. Strain, ltochester, N. in, assignors to Eastman lflodalr Company, toehester, N. Y, a corporation or New iiersey l lo lll rarling.

Application Uctober ll, i939,

Serial No. 293,95il

, l3 @laiine.

This invention relates to ace compounds and to fibrous materials such as cellulose organic derivatives, sills, wool, and cotton colored therewith. More particularly relates to azo compounds having the general formula:

wherein it represents a member selected from the group consisting of an aryl nucleus of the benzene series, an nucleus of the naphthah ene series, an aryl nucleus of the aaobenzene series, and an aryl nucleus of the benzene azo naphthalene series, R1 represents a member selected from the group consisting of an aryl nucleus of the benzene series, and an aryl nucleus of the naphthalene se -ies, Pt; represents a mornber selected from the group consisting of hydrogen, an allryl group, a hydroxyallryl group, an allroiiyallryl group, an ailrylene group, a cyclohexyl group, a phenyl group, and the group R3, and R3 represents a member selected from the group consisting of a pyridine nucleus joined to N by a nuclear carbon. atom which is ortho, meta, or para to the nuclear nitrogen of the r1ucleus, and a pyridine nucleus joined to N through a carbon atom of a short chain hydrocarbon group which is ortho, meta, or para to the nuclear nitrogen of the said nucleus. The various aryl nuclei may be substituted by one or more F monovalent substituents including halogen represented by chlorine, bromine, and fluorine; nitro groups; alkyl groups represented by methyl, butyl, cetyl and the like groups; ails-cry groups represented by niethoiry, ethoriy, and phenoxy groups; and acylainino groups represented by acetainino, propionylainino, butyrylarnino, and similar kind of groups. The pyridine nuclei, in addition to carrying inonovalent substituents of the above mentioned kind may also form quaternary salts with alizyl halides, phenylsulphomc acid allryl esters, and similar kind or salt forming compounds. ltd-any or these quaternary salt dyes possess the unique property of being surface active, which enables them to act in the capacity of being their own wetting agents in various processes involving their uses. Most of the above mentioned dyes are characterized by exceptionill. Elih -15m suitable arylamines with aryl compounds having the general formula:

wherein R1, R2, and Re, have the meanings previously defined. The class of intermediates i1- lustrated by the above formula, in the case where R3 is a pyridine nucleus, may be obtained by con" densing the desired nuclear halogenated pyridines or substituted halogenated pyridines with aniline, napl'lthylaroine, or derivatives or these airlines. in the case Where he represents an alkyl pyridine, the intermediates may be obtained, for example, by condensing an aininoallryl pyridine with a phenol or a naphthol, or by condensing a haloallr lpyridinc, or a hydroiryalhyl pyridine with the dos -ed airline or" the benzene or naphthalene Oi by condensing a pyridine allryl aldehyde with the same type of an use, and reducing the product obtained in the presence of a hydrogenating catalyst.

The following examples illustrate the preparation or the arc compounds of our invention.

1 mole of o-chloroaniline is diazotized with sodium nitrite and added to 1 mole of an aqueous hydrochloric acid solution or 2-1n-to1uido pyridine. After standing. for a short time, the roixture is made alkaline with sodium acetate, and when the coupling reaction is complete, the dye is filtered oil, and dried. Cellulose acetate is colored yellow shade-s from an aqueous suspension of the dye.

The are compound obtained has the formula:

l I 01 orn Example 2 1 mole of p-aminoacetophenone is diaaotized and coupled with 1 mole of i-(butylanilino-)-2- inethylpyridine butyl bromide following the procedure of Example l. Qellulose acetate is colored orange shades from an aqueous dispersion of the The are compound has the formula:

CH3 Dyes or the above quaternary salt type have the property of being their'own wetting out agents.

this is particularly true in the cases Where the salt is formed with a higher molecular weight allryl halide such as cetyl bromide.

Example 3 1 mole of p-nitro-o-chloroaniline is diazotized with sodium nitrite and coupled as in Example 1 with 1 mole of 2-(' -hydroxypropyl-m-toluido-)-4,6-d imethyl pyridine. Cellulose acetate is colored rubine shades from an aqueous suspension of the dye.

The azo dye compound has the formula:

Example 4 1 mole of 2-amino-5-nitrophenyl methyl sulfone is diazotized and coupled as in Example 1 with 1 mole of 2-(5-hydroxy-u-naphthylamino-)-pyridinel Cellulose acetate is colored greenish-blue shades from an aqueous suspension of the dye, which has the following formula:

Example 5 1 mole of methyl anthranilate is diazotized with sodium nitrite and added with stirring to a dilute hydrochloric acid solution of 1 mole of 3 I8 hydroxyethylanilinoethyl pyridine. After standing for a short time, the mixture is neutralized with sodium carbonate, and the dye filtered out and dried. Cellulose acetate is colored yellow shades from an aqueous suspension of the dye.

The azo compound has the formula:

COOCH:

1 mole of p-nitro-o-hydroxyaniline is diazotized and coupled in the usual manner with 1 mole of 2-cresidino- -propyl pyridine, the dye compound obtained coloring cellulose acetate pinkish-red shades from an aqueous suspension of the dye, and having the formula:

Example 6 OCH3 CaH

there may be substituted the isomeric 3-cresidinopropyl pyridine, and e-cresidinopropyl pyridine.

Example 7 1 mole of 2.4-dinitro-G-bromoaniline is diazotized and coupled in'the usual manner with 1 mole of 3-(5-sulphonic acid-a-naphthylaminomethyl) pyridine, the dye compound resulting therefrom coloring silk and wool blue shades from an aqueous solution of the dye, and having the formula:

I No: HSO3 Inpla'ce-of the-above coupling component,

there may be substituted the isomeric compounds 2- (5 -sulphonic acid-a-naphthylaminomethyl) pyridine and 4-(5'-sulphonic acid-a-naphthylaminomethyl) -pyri-dine.

Example 8 in an aqueous dispersion of 1 gram of the above dyestuff in its reduced form, the fabric acquires a yellow color, which by the steps'of diazotizing with an aqueous acid solution of sodium nitrite, washing, and coupling with 2-hydroxy-3-naphthoic acid is changed to a deep black color. The dye compound formed on the fiber has the probable formula:

In place of 4-ethylanilinomethylpyridine, there may be substituted 3-ethylanilinomethylpyridine, 2-;3-hydroxyethylanilihomethylpyridine, 3-cresidinomethylpyridine, l-anilinoethylpyridine, 2- {3-hydroxyethylanilinopropyl pyridine, and similar kind of pyridine compounds.

In order that the scope of'our invention'will be morefully apparent, We are disclosing in the following table a number of additional examples of suitablediazotization and coupling components, the dyes resulting therefrom coloring cellulose acetate fibers, unless otherwise indicated for silk, wool, and cotton, the shades of color designated.

Diazotization components Coupling component 1 gsdeea%lltg%lgu- /OH: Methyl antln'zmilate 1. C N\ Yellow.

/CH3 o-Chlol-oaniline 2. N\ Do.

55 p-Nitroaniline-o-sulphonlc acid.

p-Nitro-anisidine p-Nitro-wtoluidine;

2,4-dinitroani1ine C Hz- C H:- C Hg- OH] N Cyclohaxyl Diazotization compqnents Coupling compone t sliggaeaqgtcaetlgup-Aminoucetophenone C -N\ /O=H| Oranga.

( C H I N s OH; \I 1 CzH40H p-Nitroaniline 4. N Rublna.

N CHI CaHoO CH: CH: Do 6- -N Do.

n 0 Hr- C H; LO CH: N

C H: /CHaCHOHCHaOH p-Nitro-o-chloroaniline 6- QN Do. 25

N O 1 /H 30 D0 Blue.

0 Hr C H: C H: l 35 p-Nitrmo-bromoaniline 8. ON S 020 115 Red. N

O C H! /CH2 N D0 9. N Rubina,

C2H4 N l l O OH:

D-Nitro-o-hydroxyaniline 10. N Pinkish-red.'

C 2114 0 H 50 c p-Nitro-o-methy1sulfone aml1ne 11. N\ Violet.

Colors silk and wool red.

Colors silk, wool,

and cotton, orange-red to blue.

Orange.

Violet.

Diazotization components Coupling components shade on cenu' lose acetate 2,4-dmitroamhne 16. N\ Violet.

CH: HI

/H 2,4-dinitro-6-cl11oroani1ine 17. 8N Blue. :15

OCH:

l CHzCHOHCHqOCH:

Do 8- N\ Reddish-blue. CIH(\ :20 HI /H Do 9. N\ Purple.

CH2 N 2125 H Do 20. N\ Blue-green.

3 i 30 HO N OCH: I Do "'21- -N\ V Blue. 35 CH N NHacyi OCHI l /CH:CHOHCH1OCH: 40 2,4-dinitro-G-bromoaniline 22. QN Reddish-bluo. CHI

H Benzldme 23. N Colors silk and 45 N 1 W001, orange.

/Cyciohexyl 50 D 4 N "H Colors silk and i-wool, orange- CH2 N yellow.

'SOsH CaH1 2-amino-6-methoxybenzothiazole '25 -N N Red.

, 02 50 1-am1no-8-naphthoi-4-suifonicacid. 26. N\ Blue.

N Br Cetyl .65 /C:H4OCH;

p-Aminoazobenzene 27. QN N/H Red.

"SOIC|H D 28. N\ Orange-red.

CHg- H N asset/cs,

In the application of the are compounds of our invention to the coloration of organic de-- rivatives of cellulose, sills, cotton, and wool, the dye compound may be formed on the fiber by diazotizing the desired amine and coupling with the developer in situ, or the dye compound may first be prepared in the manner described and then applied to the material to be colored from an aqueous solution or suspension of the dye. In general, the unsulionated dye compounds of our invention are adapted to coloring organic derivatives of cellulose, while the sulfonated dye products are more adapted to the coloration of natural fibers represented by sills, wool, and cotton. For the dyeing of cellulose acetate, it will be found that most of the dyes of the invention are either water-soluble or self dispersing type of quaternary salts so that they can be applied directly from an aqueous solution containing salt without the necessity of employing a dis persing or solubilizing agent. Where the particular dye compound is only slightly or moderately soluble, however, it is first ground to a paste with a dispersing agent such as a soap, a sulionated oil, or a higher fatty glyceryl sulfate, and the resulting then dispersed in water. The material to be colored is immersed in this dispersion starting with a bath temperature of approximately ill-55 and then gradually increasing the temperature to 8-d5 G2, at which point it is maintained for several hours. Sodium chloride may be added to facilitate exhaustion of the dye bath during the dyeing operation. sired shade, it is removed from the bath, washe with soap, rinsed and dried.

While our invention is illustrated more partlcularly in connection with cellulose acetate, a material to which the invention is especially 4 adapted, it will be understood that the arse dye compounds above described are not limited exclusively to cellulose acetate, but are likewise applicable for coloring organic dedvatives of cellulose in general, including both the hydrolyzed s as well as the unhydrolyzed organic acid esters oi? cellulose such as cellulose formate, cellulose acetate, cellulose propionate, cellulose butyrate,

and the hydrolyzed as well as the unhydrolyzec mixed organic acid esters of cellulose such as 50 cellulose acetate-propionate, cellulose acetatebutyrate, and cellulose others such as methyl cellulose, ethyl cellulose, and bensyl cellulose.

We claim:

l. The compounds having the general 55 formula:

R-N=N-R1N wherein R reprer ts a member from the group consistin an aryl nucleus of the zene series, ary nucleus of the naphth series, aryl nucleus of the a and an aryl nucleus of the 65 thalene series, R1 represents a in from the group consisting of the benzene series, a d an aryl nucleus of the naphthalene series, 1 represents a member h lected from the group consisting of hydrogen,

l 0 alliyl group, a hydroizyalltyl group, an allroxyallsiyl group, an allrylene group, a cyclchexyl group, a phenyl group, and the group R3, and represents a member selected from the group consisting of a pyridine nucleus joined to ll by a nuclear carbon 75 atom which is ortho, meta, or para to the nuclear When the material has acquired the de-- formula:

nitrogen of the said nucleus, and a pyridine nucleus joined to N through a carbon atom of a short chain hydrocarbon group which is ortho,

meta, or para to the nuclear nitrogen of the said nucleus.

2. The one compounds having the general formula:

R2 Rav n-BIN wherein R rcpreseiiits a member selected from the group consisting of an aryl nucleus of the benzene series, an eryl nucleus of the naphthalene series, an aryl nucleus of the azobenzene series, and an aryl nucleus of the benzene azonaphthalene series, R1 represents a member selected from the group consisting of an aryl nucleus of the henzene series, and an aryl nucleus of the naphthalene series, R2 represents a member selected from the group consisting oi hydrogen, an allryl group, a hydroxyallryl group, fiJliIOXYZtIRYI group, an allrylene group, a cyclohexyl group, a phenyl group, and the group R3, and R3 represents a pyridine nucleus joined to N by a nuclear carbon atom which is ortho, meta, or para to the nuclear nitrogen of the said nucleus.

wherein represents a member selected from the group consisting of an aryl nucleus of the benzene series, an aryl nucleus of the naphthalene series,

aryl nucleus of the azobensene series, and an aryl nucleus of the bencene azonaphthalene series, R1 represents a member selected from the group consisting of an aryl nucleus of the benzene series, and an aryl nucleus of the naphthalene series, R2 re *esents a member selected from the group consisting of hydrogen, an allryl. group, a hydroxyallryl group, an allrosyallryl' group, an alkalene group, a cycle hexyl group, a phenyl group, and the group represents a pyridine nucleus joined to N through a carbon atom of a short chain hydrocarbon group which is ortho, meta, or to the nuclear nitrogen of the said nucleus.

-4=.-The are compounds having the general wherein R and R1 each represents an aryl nucleus of the benzene series, Rare-presents a member selected from the group consisting of hydrogen, an allryl group, a hydrcxyalkyl group, an alkoxyallryl group,an allrylene group,a cyclohexyl group, a phenyl group, and the group and R3 represents a member selected from. the group consisting of a pyridine nucleus joined to N by a nuclear carbon atom which is ortho, meta, or para to the nuclear nitrogen of the said nucleus, and a pyridine nucleus joined to N through a carbon atom of a short chain hydrocarbon group which is ortho, or para to th nuclear nitrogen of the said nucleus.

5. The ,aa'o compounds having "formula:

the general wherein R and R1 each represents an aryl nucleus of the benzene series, R2 represents a member se-' lected from the group consisting of hydrogen, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylene group, a cyclohexyl group, a phenyl group, and the group R3, and Rs represents a pyridine nucleus joined to N by a nuclear carbon atom which is ortho, meta, or para to the nuclear nitrogen of the said nucleus.

6. The azo compounds having the general formula:

R: RN=NR1N/ wherein each X represents a member selected from the group consisting of hydrogen, a halogen, and a nitro group, R1 represents anaryl nucleus of the benzene series, R2 represents a member selected from the group consisting of hydrogen, an alkyl group, a'hydroxyalk-ylgroup, an alkoxyalkylgroup, an alkylene group, a cyclohexyl group, a phenyl group, and the'group R3, and R3 represents a member selected from the group consisting of a pyridinenucleus'joinedto N by a nuclear carbon atom which is ortho,. meta, or para to the nuclear nitrogen of the said nucleus, and a pyridine nucleus" joined to- N through a carbon atom of a short chain hydrocarbon group which is ortho, meta; or para tothe nuclear nitrogen of the said nucleus.

8. Material made of or containingan organic derivative of cellulose colored with a dye selected w from the class of non-sulfonated nuclear Jazo compounds having the general formula:

R: R--N=NR1'N/ wherein R represents a member selected from the groupconsisting of an aryl nucleus of 'the benzene series, an aryl nucleus of the naphthalene series, an aryl nucleus of theazobenzeneseries, and an aryl nucleus of the benzene -azo naphthalene series, R1 represents a member se-, lected from the group consisting of an .aryl nucleus of the benzene series, and an aryl nucleus of the naphthalene series, Rz representsa mem-. ber selected from the groupconsisting of :hydrogen, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylene group, .a cyclohexyl group, a phenyl group, and the-group R3,- and R3 represents a member selected irom the group consisting of a pyridine nucleus joined-to N by a nuclear carbon atom which is ortho, meta, or para to the nuclear nitrogen of the said nucleus, and a pyridine nucleusjoiried to N through a carbon atom of a short chain hydrocarbon group .which is ortho, meta, or para to the nuclear nitrogen of. the said nucleus.

9, Material made of or containing cellulose acetate colored with a dye selected from the class of non-sulfonated nuclear azo compounds having the general formula:

wherein R represents a member selected from the group consisting of an aryl nucleus of the benzene series, an aryl nucleus of the naphthalene series, an aryl nucleus of the azobenzene series, and an aryl nucleus of the benzene azo naphthalene series, R1 represents a member selected from the group consisting of an aryl nucleus of the benzene series, and an aryl nucleus of the naphthalene series, R2 represents a member selected from the group consisting of hydrogen, an alkyl group, -a hydroxyalkyl group, an alkoxyalkyl group, .an alkylene group, a cyclohexyl group, a phenyl group, and the group R3, and R3 represents a member selected from the group consistingof apyridine nucleus joined to N by a nuclearccarbon atom which is ortho, meta, or para to the nuclear nitrogen of the said nucleus, and .-a:pyridine nucleus joined to N through a carbon atomof a short chain hydrocarbon group which:is ortho, meta, or para to the nuclear nitrogen of the i saidnucleus.

10. -Material'made of or containing anorganic derivative of cellulose colored with a dye selected fromthe class of non-sulfonated' nuclear azo compounds having the general formula:

wherein-R and R1 each represents an aryl .nucleus of the benzene series,1R2 represents a member selected fromthe group consisting of hydrogen, an alkyl group, a hydroxyalkyl group, an alkoxyal-kyl group, an alkylene. group, a cyclohexyl group a phenyl group, and the group R3, andRa represents a member selected from the group-consistingof a pyridine nucleus joined to N by a nuclear carbon atom which is ortho, meta, or para to theanuclear nitrogen of the said nucleus, and a pyridine nucleus joined to N through a carbon atom of a short chain hydrocarbon groupwhich is ortho, meta, or para to the nuclear nitrogen of the said nucleus.

11. Material made of or containing cellulose acetate colored with a dye selected from the class of non-sulfonated nuclear azo compounds having the general formula:

wherein R and R1 eachrepresents an aryl nucleus of the benzene series, R2 represents a member selected fromthe'group consistingof hydrogen, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylene group, a cyclohexylgroup, a phenyl group, and the group R3, and JRaIepresentS a member'selected from the group consisting ofa pyridine nucleus joined to N-bya nuclear carbonatom which is ortho,:meta, or paraetoithetnuclearznitrogen of the said nucleus,iand a pyridine nucleus joined to N through a carbon" atom of a" short chain' hydrocarbon group which is ortho, meta, or para to the nuclear nitrogen of the said nucleus.

12. Material made of or containing an organic derivative of cellulose colored with a dye selected from the class of non-sulfonated nuclear azo compounds having the general formula:

wherein each X represents a member selected from the group consisting of hydrogen, a halogen, and a nitro group, R1 represents an aryl nucleus of the benzene series, R2 represents a member selected from the group consisting of hydrogen, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylene group, a cyclohexyl group, a phenyl group, and the group R3, and R3 represents a member selected from the group consisting of a pyridine nucleus joined to N by a nuclear carbon atom which is ortho, meta, or para to the nuclear nitrogen of the said nucleus, and a pyridine nucleus joined to N through a carbon atom of a short chain hydrocarbon group which is ortho, meta, or para to the nuclear nitrogen of the said nucleus.

3- Material made of or containing cellulose acetate colored with a dye selected from the class of non-sulfonated nuclear azo compounds having the general formula:

wherein each X represents a member selected from the group consisting of hydrogen, a halogen, and a nitro group, R1 represents an aryl nucleus of the benzene series, R2 represents a member selected from the group consisting of hydrogen, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylene group, a cyclohexyl group, a phenyl group, and the group R3, and R3 represents a member selected from the group consisting of a pyridine nucleus joined to N by a nuclear carbon atom which is ortho, meta, or para to the nuclear nitrogen of the said nucleus, and a pyridine nucleus joined to N through a carbon atom of a short chain hydrocarbon group Which is ortho, meta, or para to the nuclear nitrogen of the said nucleus.

JOSEPH B. DICKEY. WILLIAM H. STRAIN. 

